U.S. patent application number 14/655568 was filed with the patent office on 2015-12-03 for 1-(substituted-benzoyl)-5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1- h)-one derivatives.
The applicant listed for this patent is DOW AGROSCIENCES LLC. Invention is credited to Beth Lorsbach, W. John Owen, Lindsay Stelzer, Chenglin Yao.
Application Number | 20150342188 14/655568 |
Document ID | / |
Family ID | 51022027 |
Filed Date | 2015-12-03 |
United States Patent
Application |
20150342188 |
Kind Code |
A1 |
Lorsbach; Beth ; et
al. |
December 3, 2015 |
1-(SUBSTITUTED-BENZOYL)-5-FLUORO-4-IMINO-3-METHYL-3,4-DIHYDROPYRIMIDIN-2(1-
H)-ONE DERIVATIVES
Abstract
This present disclosure is related to the field of
1-(substituted-benzoyl)-5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(-
1H)-ones and their derivatives and to the use of these compounds as
fungicides. Fungicides are compounds, of natural or synthetic
origin, which act to protect and/or cure plants against damage
caused by agriculturally relevant fungi. Generally, no single
fungicide is useful in all situations. Consequently, research is
ongoing to produce fungicides that may have better performance, are
easier to use, and cost less. The present disclosure relates to
1-(substituted-benzoyl)-5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(-
1H)-one compounds and their use as fungicides. The compounds of the
present disclosure may offer protection against fungi and fungi
like organisms including ascomycetes, basidiomycetes,
deuteromycetes, and oomycetes.
Inventors: |
Lorsbach; Beth;
(Indianapolis, IN) ; Owen; W. John; (Carmel,
IN) ; Stelzer; Lindsay; (Indianapolis, IN) ;
Yao; Chenglin; (Westfield, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW AGROSCIENCES LLC |
Indianapolis |
IN |
US |
|
|
Family ID: |
51022027 |
Appl. No.: |
14/655568 |
Filed: |
December 23, 2013 |
PCT Filed: |
December 23, 2013 |
PCT NO: |
PCT/US13/77478 |
371 Date: |
June 25, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61747128 |
Dec 28, 2012 |
|
|
|
Current U.S.
Class: |
514/274 ;
544/317 |
Current CPC
Class: |
A61P 31/10 20180101;
A01N 43/54 20130101; C07D 239/47 20130101 |
International
Class: |
A01N 43/54 20060101
A01N043/54; C07D 239/47 20060101 C07D239/47 |
Claims
1. A compound of Formula I: ##STR00007## wherein R.sup.1 is
--C(.dbd.O)R.sup.4 or --C(.dbd.S)R.sup.4; R.sup.2 is
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.3-C.sub.6
alkynyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxyalkyl,
C.sub.1-C.sub.6 aminoalkyl, C.sub.2-C.sub.6 alkylcarbonyl,
arylcarbonyl, C.sub.2-C.sub.6 alkoxycarbonyl, C.sub.2-C.sub.6
alkylaminocarbonyl, --S(O).sub.2R.sup.5, phenyl or benzyl, wherein
each of the phenyl or the benzyl may be optionally substituted with
1-3 R.sup.5, or a 5- or 6-membered saturated or unsaturated ring
containing 1-3 heteroatoms, wherein each ring may be optionally
substituted with 1-3 R.sup.5; R.sup.3 is independently H,
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.3-C.sub.6
alkynyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxyalkyl,
C.sub.2-C.sub.6 alkylcarbonyl, arylcarbonyl, C.sub.2-C.sub.6
alkoxycarbonyl, C.sub.2-C.sub.6 alkylaminocarbonyl, phenyl or
benzyl, wherein each of the phenyl or the benzyl may be optionally
substituted with 1-3 R.sup.5, or a 5- or 6-membered saturated or
unsaturated ring containing 1-3 heteroatoms, wherein each ring may
be optionally substituted with 1-3 R.sup.5; R.sup.4 is
independently C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
phenyl or benzyl, wherein each of the phenyl or the benzyl may be
optionally substituted with 1-3 R.sup.5, or a 5- or 6-membered
saturated or unsaturated ring containing 1-3 heteroatoms, wherein
each ring may be optionally substituted with 1-3 R.sup.5; and
R.sup.5 is independently halogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6
haloalkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6
haloalkylthio, amino, C.sub.1-C.sub.6 alkylamino, C.sub.2-C.sub.6
alkoxycarbonyl, or C.sub.2-C.sub.6 alkylcarbonyl, hydroxyl, cyano,
or nitro.
2. The compound of Formula I, wherein the compound of Formula (I)
is selected from the group consisting of: ##STR00008##
3. A composition for the control of a fungal disease, a comprising
a composition for the control of at least one fungal disease, said
composition including a fungicidally effective amount of the
compound of Formula I and a phytologically acceptable carrier
material.
4. The composition of claim 3 wherein the fungal disease is
Septoria tritici.
5. A method for the control and prevention of fungal attack on a
plant, the method including the steps of: applying a fungicidally
effective amount of at least one of the compounds of Formula (I) of
claim 1 to at least one surface selected from the group of surfaces
selected from the group consisting of: a portion of a plant, an
area adjacent to a plant, soil in contact with a plant, soil
adjacent to a plant, any surface adjacent to a plant, any surface
in contact with a plant, a seed, and equipment used in
agriculture.
6. The method of claim 5, wherein the fungicidally effective amount
Formula I is applied to a surface in the range of about 0.01
g/m.sup.2 to about 0.45 g/m.sup.2 of Formula I.
7. The method of claim 5, wherein the wherein the compound of
Formula (I) is selected from the group consisting of: ##STR00009##
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Patent Application Ser. No. 61/747,128 filed Dec. 28, 2012, which
is expressly incorporated by reference herein.
BACKGROUND AND SUMMARY OF THE INVENTION
[0002] Fungicides are compounds, of natural or synthetic origin,
which act to protect and/or cure plants against damage caused by
agriculturally relevant fungi. Generally, no single fungicide is
useful in all situations. Consequently, research is ongoing to
produce fungicides that may have better performance, are easier to
use, and cost less.
[0003] The present disclosure relates to
1-(substituted-benzoyl)-5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(-
1H)-one compounds and their use as fungicides. The compounds of the
present disclosure may offer protection against fungi and fungi
like organisms including ascomycetes, basidiomycetes,
deuteromycetes, and oomycetes.
[0004] One embodiment of the present disclosure may include
compounds of Formula I:
##STR00001##
[0005] wherein R.sup.1 is: --C(.dbd.O)R.sup.4 or
--C(.dbd.S)R.sup.4;
[0006] R.sup.2 is: C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6
alkoxyalkyl, C.sub.1-C.sub.6 aminoalkyl, C.sub.2-C.sub.6
alkylcarbonyl, arylcarbonyl, C.sub.2-C.sub.6 alkoxycarbonyl,
C.sub.2-C.sub.6 alkylaminocarbonyl, --S(O).sub.2R.sup.5, phenyl or
benzyl, wherein each of the phenyl or the benzyl may be optionally
substituted with 1-3 R.sup.5, or a 5- or 6-membered saturated or
unsaturated ring containing 1-3 heteroatoms, wherein each ring may
be optionally substituted with 1-3 R.sup.5;
[0007] R.sup.3 is independently H, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6
haloalkyl, C.sub.1-C.sub.6 alkoxyalkyl, C.sub.2-C.sub.6
alkylcarbonyl, arylcarbonyl, C.sub.2-C.sub.6 alkoxycarbonyl,
C.sub.2-C.sub.6 alkylaminocarbonyl, phenyl or benzyl, wherein each
of the phenyl or the benzyl may be optionally substituted with 1-3
R.sup.5, or a 5- or 6-membered saturated or unsaturated ring
containing 1-3 heteroatoms, wherein each ring may be optionally
substituted with 1-3 R.sup.5;
[0008] R.sup.4 is independently C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, phenyl or benzyl, wherein each of the
phenyl or the benzyl may be optionally substituted with 1-3
R.sup.5, or a 5- or 6-membered saturated or unsaturated ring
containing 1-3 heteroatoms, wherein each ring may be optionally
substituted with 1-3 R.sup.5; and
[0009] R.sup.5 is independently halogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6
haloalkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6
haloalkylthio, amino, C.sub.1-C.sub.6 alkylamino, C.sub.2-C.sub.6
alkoxycarbonyl, or C.sub.2-C.sub.6 alkylcarbonyl, hydroxyl, cyano,
or nitro.
[0010] In some embodiments, R.sup.4 is phenyl optionally
substituted with 1-3 R.sup.5. In a more particular embodiment,
R.sup.4 is phenyl optionally substituted with 1-3 C.sub.1 alkyl or
halogen. In another more particular embodiment, R.sup.4 is phenyl
optionally substituted with a C.sub.1 alkyl or 1-2 chloro.
[0011] In some embodiments, the compound of Formula (I) is selected
from the group consisting of:
##STR00002##
[0012] Another embodiment of the present disclosure may include a
fungicidal composition for the control or prevention of fungal
attack comprising the compounds described below and a
phytologically acceptable carrier material.
[0013] Yet another embodiment of the present disclosure may include
a method for the control or prevention of fungal attack on a plant,
the method including the step of applying a fungicidally effective
amount of one or more of the compounds described below to at least
one of the fungus, the plant, an area adjacent to the plant, or the
seed adapted to produce the plant.
[0014] Still another embodiment is A composition for the control of
a fungal disease, a comprising a composition for the control of at
least one fungal disease, said composition including a fungicidally
effective amount of the compound of Formula I and a phytologically
acceptable carrier material. In some embodiments the fungal disease
is selected from the group of organisms consisting of: Venturia
inaequalis, Septoria tritici, Cercospora beticola, Cercospora
arachidicola, Cercosporidium personatuml, and Mycosphaerella
fijiensis.
[0015] Still other embodiments include methods for the control and
prevention of fungal attack on a plant, the method including the
steps of: applying a fungicidally effective amount of at least one
of the compounds of Formula 1 to at least one surface selected from
the group of surfaces selected from the group consisting of: a
portion of a plant, an area adjacent to a plant, soil in contact
with a plant, soil adjacent to a plant, any surface adjacent to a
plant, any surface in contact with a plant, a seed, and equipment
used in agriculture. In some embodiments a fungicidally effective
amount of Formula I is applied in the range of about 0.01 g/m.sup.2
to about 0.45 g/m.sup.2 of Formula I.
[0016] The term "alkyl" refers to a branched, unbranched, or cyclic
carbon chain, including methyl, ethyl, propyl, butyl, isopropyl,
isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl and the like.
[0017] The term "alkenyl" refers to a branched, unbranched or
cyclic carbon chain containing one or more double bonds, including
ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclohexenyl,
and the like.
[0018] The term "alkynyl" refers to a branched or unbranched carbon
chain containing one or more triple bonds, including propynyl,
butynyl and the like.
[0019] As used throughout this specification, the term `R` refers
to the group consisting of C.sub.1-8 alkyl, C.sub.3-8 alkenyl or
C.sub.3-8 alkynyl, unless stated otherwise.
[0020] The term "alkoxy" refers to an --OR substituent.
[0021] The term "alkoxycarbonyl" refers to a --C(O)--OR
substituent.
[0022] The term "alkylcarbonyl" refers to a --C(O)--R
substituent.
[0023] The term "arylcarbonyl" refers to a --C(O)--R substituent,
where R is either phenyl, wherein the phenyl may be optionally
substituted with 1-3 R.sup.5, or a 5- or 6-membered saturated or
unsaturated ring containing 1-3 heteroatoms, wherein each ring may
be optionally substituted with 1-3 R.sup.5.
[0024] The term "alkylsulfonyl" refers to an --SO.sub.2--R
substituent.
[0025] The term "alkylthio" refers to an --S--R substituent.
[0026] The term "halothio" refers to a sulfur substituted with
three or five F substituents.
[0027] The term "haloalkylthio" refers to an alkylthio, which is
substituted with Cl, F, I, or Br or any combination thereof.
[0028] The term "alkylaminocarbonyl" refers to a --C(O)--N(H)--R
substituent.
[0029] The term "trialkylsilyl" refers to --SiR.sub.3.
[0030] The term "cyano" refers to a --C.ident.N substituent.
[0031] The term "hydroxyl" refers to an --OH substituent.
[0032] The term "amino" refers to a --NH.sub.2 substituent.
[0033] The term "alkylamino" refers to a --N(H)--R substituent.
[0034] The term "dialkylamino" refers to a --NR.sub.2
substituent.
[0035] The term "alkoxyalkyl" refers to an alkoxy substitution on
an alkyl.
[0036] The term "halogen" or "halo" refers to one or more halogen
atoms, defined as F, Cl, Br, and I.
[0037] The term "nitro" refers to a --NO.sub.2 substituent.
[0038] Unless specifically noted or clearly implied otherwise the
term "about" refers to a range of values of plus or minus 10
percent, e.g. about 1 refers to the range 0.9 to 1.1.
[0039] Throughout the disclosure, reference to the compounds of
Formula I is read as also including optical isomers and salts of
Formula I, and hydrates thereof. Specifically, when Formula I
contains a branched chain alkyl group, it is understood that such
compounds include optical isomers and racemates thereof. Exemplary
salts include: hydrochloride, hydrobromide, hydroiodide, and the
like. Additionally, the compounds of Formula I may include
tautomeric forms.
[0040] Certain compounds disclosed in this document can exist as
one or more isomers. It will be appreciated by those skilled in the
art that one isomer may be more active than the others. The
structures disclosed in the present disclosure are drawn in only
one geometric form for clarity, but are intended to represent all
geometric and tautomeric forms of the molecule.
[0041] It is also understood by those skilled in the art that
additional substitution is allowable, unless otherwise noted, as
long as the rules of chemical bonding and strain energy are
satisfied and the product still exhibits fungicidal activity.
[0042] Another embodiment of the present disclosure is a use of a
compound of Formula I, for protection of a plant against attack by
a phytopathogenic organism or the treatment of a plant infested by
a phytopathogenic organism, comprising the application of a
compound of Formula I, or a composition comprising the compound to
soil, a plant, a part of a plant, foliage, and/or seeds.
[0043] Additionally, another embodiment of the present disclosure
is a composition useful for protecting a plant against attack by a
phytopathogenic organism and/or treatment of a plant infested by a
phytopathogenic organism comprising a compound of Formula I and a
phytologically acceptable carrier material.
[0044] Additional features and advantages of the present invention
will become apparent to those skilled in the art upon consideration
of the following detailed description of the illustrative
embodiments exemplifying the best mode of carrying out the
invention as presently perceived.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0045] The compounds of the present disclosure may be applied by
any of a variety of known techniques, either as the compounds or as
formulations comprising the compounds. For example, the compounds
may be applied to the roots, seeds or foliage of plants for the
control of various fungi, without damaging the commercial value of
the plants. The materials may be applied in the form of any of the
generally used formulation types, for example, as solutions, dusts,
wettable powders, flowable concentrates, suspension concentrates or
emulsifiable concentrates.
[0046] Preferably, the compounds of the present disclosure are
applied in the form of a formulation, comprising one or more of the
compounds of Formula I with a phytologically acceptable carrier.
Concentrated formulations may be dispersed in water, or other
liquids, for application, or formulations may be dust-like or
granular, which may then be applied without further treatment. The
formulations can be prepared according to procedures that are
conventional in the agricultural chemical art.
[0047] The present disclosure contemplates all vehicles by which
one or more of the compounds may be formulated for delivery and use
as a fungicide. Typically, formulations are applied as aqueous
suspensions or emulsions. Such suspensions or emulsions may be
produced from water-soluble, water-suspendible, or emulsifiable
formulations which are solids, usually known as wettable powders;
or liquids, usually known as emulsifiable concentrates, aqueous
suspensions, or suspension concentrates. As will be readily
appreciated, any material to which these compounds may be added may
be used, provided it yields the desired utility without significant
interference with the activity of these compounds as antifungal
agents.
[0048] Wettable powders, which may be compacted to form water
dispersible granules, comprise an intimate mixture of one or more
of the compounds of Formula I, an inert carrier and surfactants.
The concentration of the compound in the wettable powder may be
from about 10 percent to about 90 percent by weight based on the
total weight of the wettable powder, more preferably about 25
weight percent to about 75 weight percent. In the preparation of
wettable powder formulations, the compounds may be compounded with
any finely divided solid, such as prophyllite, talc, chalk, gypsum,
Fuller's earth, bentonite, attapulgite, starch, casein, gluten,
montmorillonite clays, diatomaceous earths, purified silicates or
the like. In such operations, the finely divided carrier and
surfactants are typically blended with the compound(s) and
milled.
[0049] Emulsifiable concentrates of the compounds of Formula I may
comprise a convenient concentration, such as from about 10 weight
percent to about 50 weight percent of the compound, in a suitable
liquid, based on the total weight of the concentrate. The compounds
may be dissolved in an inert carrier, which is either a
water-miscible solvent or a mixture of water-immiscible organic
solvents, and emulsifiers. The concentrates may be diluted with
water and oil to form spray mixtures in the form of oil-in-water
emulsions. Useful organic solvents include aromatics, especially
the high-boiling naphthalenic and olefinic portions of petroleum
such as heavy aromatic naphtha. Other organic solvents may also be
used, for example, terpenic solvents, including rosin derivatives,
aliphatic ketones, such as cyclohexanone, and complex alcohols,
such as 2-ethoxyethanol.
[0050] Emulsifiers which may be advantageously employed herein may
be readily determined by those skilled in the art and include
various nonionic, anionic, cationic and amphoteric emulsifiers, or
a blend of two or more emulsifiers. Examples of nonionic
emulsifiers useful in preparing the emulsifiable concentrates
include the polyalkylene glycol ethers and condensation products of
alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or
fatty acids with ethylene oxide, propylene oxides such as the
ethoxylated alkyl phenols and carboxylic esters solubilized with
the polyol or polyoxyalkylene. Cationic emulsifiers include
quaternary ammonium compounds and fatty amine salts. Anionic
emulsifiers include the oil-soluble salts (e.g., calcium) of
alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol
ethers and appropriate salts of phosphated polyglycol ether.
[0051] Representative organic liquids which may be employed in
preparing the emulsifiable concentrates of the compounds of the
present invention are the aromatic liquids such as xylene, propyl
benzene fractions; or mixed naphthalene fractions, mineral oils,
substituted aromatic organic liquids such as dioctyl phthalate;
kerosene; dialkyl amides of various fatty acids, particularly the
dimethyl amides of fatty glycols and glycol derivatives such as the
n-butyl ether, ethyl ether or methyl ether of diethylene glycol,
the methyl ether of triethylene glycol, petroleum fractions or
hydrocarbons such as mineral oil, aromatic solvents, paraffinic
oils, and the like; vegetable oils such as soybean oil, rapeseed
oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn
oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower
oil, sesame oil, tung oil and the like; esters of the above
vegetable oils; and the like. Mixtures of two or more organic
liquids may also be employed in the preparation of the emulsifiable
concentrate. Organic liquids include xylene, and propyl benzene
fractions, with xylene being most preferred in some cases.
Surface-active dispersing agents are typically employed in liquid
formulations and in an amount of from 0.1 to 20 percent by weight
based on the combined weight of the dispersing agent with one or
more of the compounds. The formulations can also contain other
compatible additives, for example, plant growth regulators and
other biologically active compounds used in agriculture.
[0052] Aqueous suspensions comprise suspensions of one or more
water-insoluble compounds of Formula I, dispersed in an aqueous
vehicle at a concentration in the range from about 5 to about 50
weight percent, based on the total weight of the aqueous
suspension. Suspensions are prepared by finely grinding one or more
of the compounds, and vigorously mixing the ground material into a
vehicle comprised of water and surfactants chosen from the same
types discussed above. Other components, such as inorganic salts
and synthetic or natural gums, may also be added to increase the
density and viscosity of the aqueous vehicle. It is often most
effective to grind and mix at the same time by preparing the
aqueous mixture and homogenizing it in an implement such as a sand
mill, ball mill, or piston-type homogenizer.
[0053] Aqueous emulsions comprise emulsions of one or more
water-insoluble pesticidally active ingredients emulsified in an
aqueous vehicle at a concentration typically in the range from
about 5 to about 50 weight percent, based on the total weight of
the aqueous emulsion. If the pesticidally active ingredient is a
solid it must be dissolved in a suitable water-immiscible solvent
prior to the preparation of the aqueous emulsion. Emulsions are
prepared by emulsifying the liquid pesticidally active ingredient
or water-immiscible solution thereof into an aqueous medium
typically with inclusion of surfactants that aid in the formation
and stabilization of the emulsion as described above. This is often
accomplished with the aid of vigorous mixing provided by high shear
mixers or homogenizers.
[0054] The compounds of Formula I can also be applied as granular
formulations, which are particularly useful for applications to the
soil. Granular formulations generally contain from about 0.5 to
about 10 weight percent, based on the total weight of the granular
formulation of the compound(s), dispersed in an inert carrier which
consists entirely or in large part of coarsely divided inert
material such as attapulgite, bentonite, diatomite, clay or a
similar inexpensive substance. Such formulations are usually
prepared by dissolving the compounds in a suitable solvent and
applying it to a granular carrier which has been preformed to the
appropriate particle size, in the range of from about 0.5 to about
3 mm. A suitable solvent is a solvent in which the compound is
substantially or completely soluble. Such formulations may also be
prepared by making a dough or paste of the carrier and the compound
and solvent, and crushing and drying to obtain the desired granular
particle.
[0055] Dusts containing the compounds of Formula I may be prepared
by intimately mixing one or more of the compounds in powdered form
with a suitable dusty agricultural carrier, such as, for example,
kaolin clay, ground volcanic rock, and the like. Dusts can suitably
contain from about 1 to about 10 weight percent of the compounds,
based on the total weight of the dust.
[0056] The formulations may additionally contain adjuvant
surfactants to enhance deposition, wetting and penetration of the
compounds onto the target crop and organism. These adjuvant
surfactants may optionally be employed as a component of the
formulation or as a tank mix. The amount of adjuvant surfactant
will typically vary from 0.01 to 1.0 percent by volume, based on a
spray-volume of water, preferably 0.05 to 0.5 volume percent.
Suitable adjuvant surfactants include, but are not limited to
ethoxylated nonyl phenols, ethoxylated synthetic or natural
alcohols, salts of the esters or sulfosuccinic acids, ethoxylated
organosilicones, ethoxylated fatty amines, blends of surfactants
with mineral or vegetable oils, crop oil concentrate (mineral oil
(85%)+emulsifiers (15%)); nonylphenol ethoxylate;
benzylcocoalkyldimethyl quaternary ammonium salt; blend of
petroleum hydrocarbon, alkyl esters, organic acid, and anionic
surfactant; C.sub.9-C.sub.11 alkylpolyglycoside; phosphated alcohol
ethoxylate; natural primary alcohol (C.sub.12-C.sub.16) ethoxylate;
di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap;
nonylphenol ethoxylate+urea ammonium nitrrate; emulsified
methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO);
tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The
formulations may also include oil-in-water emulsions such as those
disclosed in U.S. patent application Ser. No. 11/495,228, the
disclosure of which is expressly incorporated by reference
herein.
[0057] The formulations may optionally include combinations that
contain other pesticidal compounds. Such additional pesticidal
compounds may be fungicides, insecticides, herbicides, nematocides,
miticides, arthropodicides, bactericides or combinations thereof
that are compatible with the compounds of the present invention in
the medium selected for application, and not antagonistic to the
activity of the present compounds. Accordingly, in such
embodiments, the other pesticidal compound is employed as a
supplemental toxicant for the same or for a different pesticidal
use. The compounds of Formula I and the pesticidal compound in the
combination can generally be present in a weight ratio of from
1:100 to 100:1.
[0058] The compounds of the present disclosure may also be combined
with other fungicides to form fungicidal mixtures and synergistic
mixtures thereof. The fungicidal compounds of the present
disclosure are often applied in conjunction with one or more other
fungicides to control a wider variety of undesirable diseases. When
used in conjunction with other fungicide(s), the presently claimed
compounds may be formulated with the other fungicide(s), tank-mixed
with the other fungicide(s) or applied sequentially with the other
fungicide(s). Such other fungicides may include
(RS)--N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,
1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone
hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,
2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,
2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,
2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,
2-methoxyethylmercury silicate,
3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenyl
thiocyanateme, N-3,5-dichlorophenyl-succinimide,
N-3-nitrophenylitaconimide,
2-(thiocyanatomethylthio)-benzothiazole, (3-ethoxypropyl)mercury
bromide, 2-methoxyethylmercury chloride, 2-phenylphenol,
8-hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline,
acibenzolar, acibenzolar-S-methyl, acypetacs, acypetacs-copper,
acypetacs-zinc, albendazole, aldimorph, allicin, allyl alcohol,
ametoctradin, amisulbrom, amobam, Ampelomyces quisqualis,
ampropylfos, anilazine, antimycin, asomate, aureofungin,
azaconazole, azithiram, azoxystrobin, Bacillus subtilis, Bacillus
subtilis strain QST713, barium polysulfide, Bayer 32394, benalaxyl,
benalaxyl-M, benquinox, benodanil, benomyl, bentaluron,
benthiavalicarb, benthiavalicarb-isopropyl, benthiazole,
benzamacril, benzamacril-isobutyl, benzamorf, benzohydroxamic acid,
benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt,
berberine, berberine chloride, bethoxazin, bicarbonates,
bifujunzhi, binapacryl, biphenyl, bismerthiazol, bis(methylmercury)
sulfate, bis(tributyltin) oxide, bitertanol, bithionol, bixafen,
blasticidin-S, borax, Bordeaux mixture, boscalid, bromothalonil,
bromuconazole, bupirimate, Burgundy mixture, buthiobate,
butylamine, cadmium calcium copper zinc chromate sulfate, calcium
polysulfide, Candida oleophila, captafol, captan, carbamorph,
carbendazim, carbendazim benzenesulfonate, carbendazim sulfite,
carboxin, carpropamid, carvacrol, carvone, CECA, Cheshunt mixture,
chinomethionat, chitosan, chlazafenone, chlobenthiazone,
chloraniformethan, chloranil, chlorfenazole,
chlorodinitronaphthalenes, chlorquinox, chloroneb, chloropicrin,
chlorothalonil, chlozolinate, climbazole, clotrimazole,
Coniothyrium minitans, copper acetate, copper
bis(3-phenylsalicylate), copper carbonate, basic, copper hydroxide,
copper naphthenate, copper octanoate, copper oleate, copper
oxychloride, copper silicate, copper sulfate, copper sulfate
(tribasic), copper zinc chromate, coumoxystrobin, cresol, cufraneb,
cupric hydrazinium sulfate, cuprobam, cuprous oxide, cyazofamid,
cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole,
cyproconazole, cyprodinil, cyprofuram, dazomet, dazomet-sodium,
DBCP, debacarb, decafentin, dehydroacetic acid, diammonium
ethylenebis-(dithiocarbamate), dichlofluanid, dichlone, dichloran,
dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine,
diclomezine-sodium, diethofencarb, diethyl pyrocarbonate,
difenoconazole, difenzoquat ion, diflumetorim, dimetachlone,
dimethirimol, dimethomorph, dimoxystrobin, dingjunezuo,
diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4,
dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon,
diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon,
dithioether, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,
dodemorph, dodemorph acetate, dodicin, dodicin hydrochloride,
dodicin-sodium, dodine, dodine free base, drazoxolon, EBP,
edifenphos, enestrobin, enestroburin, enoxastrobin, epoxiconazole,
ESBP, etaconazole, etem, ethaboxam, ethirim, ethirimol, ethoxyquin,
ethirimol, ethylmercury 2,3-dihydroxypropyl mercaptide,
ethylmercury acetate, ethylmercury bromide, ethylmercury chloride,
ethylmercury phosphate, etridiazole, famoxadone, fenamidone,
fenaminosulf, fenaminstrobin, fenapanil, fenarimol, fenbuconazole,
fenfuram, fenhexamid, fenitropan, fenjuntong, fenoxanil,
fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin,
fentin acetate, fentin chloride, fentin hydroxide, ferbam,
ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumetover,
flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole,
fluoxastrobin, fluquinconazole, flusilazole, flusulfamide,
fluthiacet-methyl, flutianil, flutolanil, flutriafol, fluxapyroxad,
folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole,
furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis,
furfural, furmecyclox, furophanate, Fusarium oxysporum, Gliocladium
spp., glyodine, griseofulvin, guazatine, guazatine acetates, GY-81,
halacrinate, Hercules 3944, hexachlorobenzene, hexachlorobutadiene,
hexachlorophene, hexaconazole, hexylthiofos, huanjunzuo,
hydrargaphen, hymexazol, ICIA0858, imazalil, imazalil nitrate,
imazalil sulfate, imibenconazole, iminoctadine, iminoctadine
triacetate, iminoctadine tris(albesilate), inezin, iodocarb,
iodomethane, ipconazole, ipfenpyrazolone, iprobenfos, iprodione,
iprovalicarb, isopamphos, isoprothiolane, isopyrazam, isotianil,
isovaledione, jiaxiangjunzhi, kasugamycin, kasugamycin
hydrochloride hydrate, kejunlin, kresoxim-methyl, laminarin,
lvdingjunzhi, mancopper, mancozeb, mandipropamid, maneb, mebenil,
mecarbinzid, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap,
mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl,
metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium,
metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl
bromide, methyl iodide, methyl isothiocyanate, methylmercury
benzoate, methylmercury dicyandiamide, methylmercury
pentachlorophenoxide, metiram, metominostrobin, metrafenone,
metsulfovax, mildiomycin, milneb, moroxydine, moroxydine
hydrochloride, mucochloric anhydride, myclobutanil, myclozolin,
N-ethylmercurio-4-toluenesulfonanilide,
N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nickel
bis(dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl,
nuarimol, OCH, octhilinone, ofurace, oleic acid (fatty acids),
orysastrobin, osthol, oxadixyl, oxathiapiprolin, oxine-copper,
oxpoconazole fumarate, oxycarboxin, parinol, pefurazoate,
penconazole, pencycuron, penflufen, pentachlorophenol,
pentachlorophenyl laurate, penthiopyrad, phenamacril,
phenylmercuriurea, phenylmercury acetate, phenylmercury chloride,
phenylmercury derivative of pyrocatechol, phenylmercury
dimethyldithiocarbamate, phenylmercury nitrate, phenylmercury
salicylate, Phlebiopsis gigantea, phosdiphen, phosphonic acid,
phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin B,
polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassium
bicarbonate, potassium hydroxyquinoline sulfate, potassium
polysulfide, potassium thiocyanate, probenazole, prochloraz,
prochloraz-manganese, procymidone, propamidine, propamidine
dihydrochloride, propamocarb, propamocarb hydrochloride,
propiconazole, propineb, proquinazid, prothiocarb, prothiocarb
hydrochloride, prothioconazole, pyracarbolid, pyraclostrobin,
pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb,
pyributicarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone,
pyrisoxazole, pyroquilon, pyroxychlor, pyroxyfur, quinacetol,
quinacetol sulfate, quinazamid, quinoclamine, quinconazole,
quinoxyfen, quintozene, rabenzazole, Reynoutria sachalinensis
extract, saisentong, salicylanilide, santonin, sedaxane,
silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium azide,
sodium bicarbonate, sodium orthophenylphenoxide, sodium
pentachlorophenoxide, sodium polysulfide, spiroxamine, Streptomyces
griseoviridis, streptomycin, streptomycin sesquisulfate, SSF-109,
sulfur, sultropen, SYP-Z048, tar oils, tebuconazole, tebufloquin,
tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole,
thiadifluor, thicyofen, thifluzamide, thiochlorfenphim,
thiodiazole-copper, thiomersal, thiophanate, thiophanate-methyl,
thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl,
tolylfluanid, tolylmercury acetate, triadimefon, triadimenol,
triamiphos, triarimol, triazbutil, triazoxide, tributyltin oxide,
trichlamide, triclopyricarb, Trichoderma spp., tricyclazole,
tridemorph, trifloxystrobin, triflumizole, triforine,
triticonazole, uniconazole, uniconazole-P, urbacid, validamycin,
valifenalate, valiphenal, vangard, vinclozolin, xiwojunan,
zarilamid, zineb, zinc naphthenate, zinc thiazole, ziram, and
zoxamide, and any combinations thereof.
[0059] Additionally, the compounds of the present invention may be
combined with other pesticides, including insecticides,
nematocides, miticides, arthropodicides, bactericides or
combinations thereof that are compatible with the compounds of the
present invention in the medium selected for application, and not
antagonistic to the activity of the present compounds to form
pesticidal mixtures and synergistic mixtures thereof. The
fungicidal compounds of the present disclosure may be applied in
conjunction with one or more other pesticides to control a wider
variety of undesirable pests. When used in conjunction with other
pesticides, the presently claimed compounds may be formulated with
the other pesticide(s), tank mixed with the other pesticide(s) or
applied sequentially with the other pesticide(s). Typical
insecticides include, but are not limited to: 1,2-dichloropropane,
abamectin, acephate, acetamiprid, acethion, acetoprole,
acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb,
aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin,
alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton,
amiton oxalate, amitraz, anabasine, athidathion, azadirachtin,
azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium
hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap,
beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin,
bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid,
bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl,
bufencarb, buprofezin, butacarb, butathiofos, butocarboxim,
butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium
polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon
disulfide, carbon tetrachloride, carbophenothion, carbosulfan,
cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen,
chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride,
chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,
chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos,
chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide,
cinerin I, cinerin II, cinerins, cismethrin, cloethocarb,
closantel, clothianidin, copper acetoarsenite, copper arsenate,
copper naphthenate, copper oleate, coumaphos, coumithoate,
crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos,
cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin,
cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine,
cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O,
demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl,
demeton-S, demeton-S-methyl, demeton-S-methylsulphon,
diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,
dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil,
dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan,
dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex,
dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan,
dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos,
d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,
doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC,
empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,
eprinomectin, esdepallethrine, esfenvalerate, etaphos,
ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl
formate, ethyl-DDD, ethylene dibromide, ethylene dichloride,
ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos,
fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion,
fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin,
fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil,
flonicamid, flubendiamide, flucofuron, flucycloxuron,
flucythrinate, flufenerim, flufenoxuron, flufenprox, flufiprole,
fluvalinate, fonofos, formetanate, formetanate hydrochloride,
formothion, formparanate, formparanate hydrochloride, fosmethilan,
fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin,
gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor,
heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,
hydrogen cyanide, hydroprene, hyquincarb, imidacloprid,
imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan,
isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb,
isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I,
jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II,
juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead
arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron,
lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon,
menazon, meperfluthrin, mephosfolan, mercurous chloride,
mesulfenfos, metaflumizone, methacrifos, methamidophos,
methidathion, methiocarb, methocrotophos, methomyl, methoprene,
methoxychlor, methoxyfenozide, methyl bromide, methyl
isothiocyanate, methylchloroform, methylene chloride, metofluthrin,
metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin,
milbemycin oxime, mipafox, mirex, molosultap, monocrotophos,
monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled,
naphthalene, nicotine, nifluridide, nitenpyram, nithiazine,
nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,
oxydemeton-methyl, oxydeprofos, oxydisulfoton,
para-dichlorobenzene, parathion, parathion-methyl, penfluron,
pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate,
phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon,
phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb,
pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium
thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II,
precocene III, primidophos, profenofos, profluralin, promacyl,
promecarb, propaphos, propetamphos, propoxur, prothidathion,
prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole,
pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins,
pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon,
pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia,
quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin,
rotenone, ryania, sabadilla, schradan, selamectin, silafluofen,
silica gel, sodium arsenite, sodium fluoride, sodium
hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram,
spinosad, spiromesifen, spirotetramat, sulcofuron,
sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl
fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide,
tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos,
TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos,
tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid,
thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam
oxalate, thiodicarb, thiofanox, thiometon, thiosultap,
thiosultap-disodium, thiosultap-monosodium, thuringiensin,
tolfenpyrad, tralomethrin, transfluthrin, transpermethrin,
triarathene, triazamate, triazophos, trichlorfon,
trichlormetaphos-3, trichloronat, trifenofos, triflumuron,
trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb,
zeta-cypermethrin, zolaprofos, and any combinations thereof.
[0060] Additionally, the compounds of the present invention may be
combined with herbicides that are compatible with the compounds of
the present invention in the medium selected for application, and
not antagonistic to the activity of the present compounds to form
pesticidal mixtures and synergistic mixtures thereof. The
fungicidal compounds of the present disclosure may be applied in
conjunction with one or more herbicides to control a wide variety
of undesirable plants. When used in conjunction with herbicides,
the presently claimed compounds may be formulated with the
herbicide(s), tank mixed with the herbicide(s) or applied
sequentially with the herbicide(s). Typical herbicides include, but
are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 2,4-D choline salt,
2,4-D esters and amines; 2,4-DB; 3,4-DA; 3,4-DB; 2,4-DEB; 2,4-DEP;
3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen,
aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl
alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone,
amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl,
amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton,
atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC,
beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate,
bensulfuron-methyl, bensulide, benthiocarb, bentazon-sodium,
benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap,
benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox,
bilanafos, bispyribac-sodium, borax, bromacil, bromobonil,
bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor,
butafenacil, butamifos, butenachlor, buthidazole, buthiuron,
butralin, butroxydim, buturon, butylate, cacodylic acid,
cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor,
carbasulam, carbetamide, carboxazole chlorprocarb,
carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben,
chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam,
chloreturon, chlorfenac, chlorfenprop, chlorflurazole,
chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon,
chlorotoluron, chloroxuron, chloroxynil, chlorpropham,
chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,
cinosulfuron, cisanilide, clethodim, cliodinate,
clodinafop-propargyl, clofop, clomazone, clomeprop, cloprop,
cloproxydim, clopyralid, cloransulam-methyl, CMA, copper sulfate,
CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine,
cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop-butyl,
cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon,
dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba,
dichlobenil, dichloralurea, dichlormate, dichlorprop,
dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl,
difenopenten, difenoxuron, difenzoquat, diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon,
dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb,
diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA,
DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon,
esprocarb, ethalfluralin, ethbenzamide, ethametsulfuron,
ethidimuron, ethiolate, ethobenzamid, etobenzamid, ethofumesate,
ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD,
fenasulam, fenoprop, fenoxaprop, fenoxaprop-P-ethyl,
fenoxaprop-P-ethyl+isoxadifen-ethyl, fenoxasulfone, fenteracol,
fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop,
flamprop-M, flazasulfuron, florasulam, fluazifop,
fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron,
fluchloralin, flufenacet, flufenican, flufenpyr-ethyl, flumetsulam,
flumezin, flumiclorac-pentyl, flumioxazin, flumipropyn,
fluometuron, fluorodifen, fluoroglycofen, fluoromidine,
fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate,
flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone,
fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen,
glufosinate, glufosinate-ammonium, glyphosate, halauxifen,
halosafen, halosulfuron-methyl, haloxydine, haloxyfop-methyl,
haloxyfop-P-methyl, hexachloroacetone, hexaflurate, hexazinone,
imazamethabenz, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil,
iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine,
ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin,
isonoruron, isopolinate, isopropalin, isoproturon, isouron,
isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate,
ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, esters
and amines, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb,
mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione,
metam, metamifop, metamitron, metazachlor, metazosulfuron,
metflurazon, methabenzthiazuron, methalpropalin, methazole,
methiobencarb, methiozolin, methiuron, methometon, methoprotryne,
methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron,
metobromuron, metolachlor, metosulam, metoxuron, metribuzin,
metsulfuron, molinate, monalide, monisouron, monochloroacetic acid,
monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide,
naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen,
nitrofluorfen, norflurazon, noruron, OCH, orbencarb,
ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl,
oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen,
paraflufen-ethyl, parafluron, paraquat, pebulate, pelargonic acid,
pendimethalin, penoxsulam, pentachlorophenol, pentanochlor,
pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham,
phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram,
picolinafen, pinoxaden, piperophos, potassium arsenite, potassium
azide, potassium cyanate, pretilachlor, primisulfuron-methyl,
procyazine, prodiamine, profluazol, profluralin, profoxydim,
proglinazine, prohexadione-calcium, prometon, prometryn,
propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propoxycarbazone, propyrisulfuron, propyzamide,
prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor,
pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazogyl,
pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim,
pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid,
pyriminobac, pyrimisulfan, pyrithiobac-methyl, pyroxasulfone,
pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid,
quizalofop, quizalofop-P-ethyl, rhodethanil, rimsulfuron,
saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim,
siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium
azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone,
sulfometuron, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin,
swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione,
tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,
terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron,
thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl,
thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone,
tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam,
tribenuron, tricamba, triclopyr esters and amines, tridiphane,
trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop,
trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,
tritosulfuron, vernolate and xylachlor.
[0061] Another embodiment of the present disclosure is a method for
the control or prevention of fungal attack. This method comprises
applying to the soil, plant, roots, foliage, seed or locus of the
fungus, or to a locus in which the infestation is to be prevented
(for example applying to cereal plants), a fungicidally effective
amount of one or more of the compounds of Formula I. The compounds
are suitable for treatment of various plants at fungicidal levels,
while exhibiting low phytotoxicity. The compounds may be useful
both in a protectant and/or an eradicant fashion.
[0062] The compounds have been found to have significant fungicidal
effect particularly for agricultural use. Many of the compounds are
particularly effective for use with agricultural crops and
horticultural plants. Additional benefits may include, but are not
limited to, improving the health of a plant; improving the yield of
a plant (e.g. increased biomass and/or increased content of
valuable ingredients); improving the vigor of a plant (e.g.
improved plant growth and/or greener leaves); improving the quality
of a plant (e.g. improved content or composition of certain
ingredients); and improving the tolerance to abiotic and/or biotic
stress of the plant.
[0063] It will be understood by those in the art that the efficacy
of the compound for the foregoing fungi establishes the general
utility of the compounds as fungicides.
[0064] The compounds have broad ranges of activity against fungal
pathogens. Exemplary pathogens may include, but are not limited to,
wheat leaf blotch (Mycosphaerella graminicola; anamorph: Septoria
tritici), apple scab (Venturia inaequalis), Cercospora leaf spots
of sugar beets (Cercospora beticola), leaf spots of peanut
(Cercospora arachidicola and Cercosporidium personatum), and black
sigatoka of bananas (Mycosphaerella fijiensis). The exact amount of
the active material to be applied is dependent not only on the
specific active material being applied, but also on the particular
action desired, the fungal species to be controlled, and the stage
of growth thereof, as well as the part of the plant or other
product to be contacted with the compound. Thus, all the compounds,
and formulations containing the same, may not be equally effective
at similar concentrations or against the same fungal species.
[0065] The compounds are effective in use with plants in a
disease-inhibiting and phytologically acceptable amount. The term
"disease-inhibiting and phytologically acceptable amount" refers to
an amount of a compound that kills or inhibits the plant disease
for which control is desired, but is not significantly toxic to the
plant. This amount will generally be from about 0.1 to about 1000
ppm (parts per million), with 1 to 500 ppm being preferred. The
exact amount of a compound required varies with the fungal disease
to be controlled, the type of formulation employed, the method of
application, the particular plant species, climate conditions, and
the like. A suitable application rate is typically in the range
from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams
per square meter, g/m.sup.2). Fungicidally effective amount of the
compounds include amounts sufficient to kill or control true fungi,
pseudo-fungi, and related organisms including water moulds.
[0066] Any range or desired value given herein may be extended or
altered without losing the effects sought, as is apparent to the
skilled person for an understanding of the teachings herein.
[0067] The compounds of Formula I may be made using well-known
chemical procedures. Intermediates not specifically mentioned in
this disclosure are either commercially available, may be made by
routes disclosed in the chemical literature, or may be readily
synthesized from commercial starting materials utilizing standard
procedures.
[0068] The following examples are presented to illustrate the
various aspects of the compounds of the present disclosure and
should not be construed as limitations to the claims.
EXAMPLE 1
Preparation of
5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one
##STR00003##
[0069] Step 1: Preparation of
4-Amino-5-fluoro-1-(4-methoxyphenylsulfonyl)pyrimidin-2(1H)-one
(I-1)
[0070] To commercially available 4-amino-5-fluoro-pyrimidin-2-ol
(1.0 grams (g), 7.75 millimoles (mmol)) in acetonitrile
(CH.sub.3CN; 50 milliliters (mL)) was added
bis-N,O-trimethylsilylacetamide (BSA; 5.7 mL, 23 3 mmol) and the
mixture was heated at 70.degree. C. for 1 hour (h), resulting in a
clear solution. After cooling to room temperature,
4-methoxybenzene-1-sulfonyl chloride (1.8 g, 8.5 mmol) was added,
and the mixture was stirred for 24 h. The solvent was evaporated
and the residue was partitioned between ethyl acetate (EtOAc) and
brine. The organic phase was dried over magnesium sulfate
(MgSO.sub.4), filtered, and evaporated to yield the product as a
pale yellow solid (1.48 g, 64%): mp 182-185.degree. C.; .sup.1H NMR
(300 MHz, CDCl.sub.3) .delta. 8.40 (br s, 1H), 8.11 (d, J=5.9 Hz,
1H), 8.04-7.98 (m, 2H), 7.02-6.96 (m, 2H), 5.77 (br s, 1H), 3.88
(s, 3H); ESIMS m/z 300 ([M+H].sup.+).
Step 2: Preparation of
5-Fluoro-4-imino-1-(4-methoxyphenylsulfonyl)-3-methyl-3,4-dihydropyrimidi-
n-2(1H)-one (I-2)
[0071] To an 8-mL screw capped vial were added
4-amino-5-fluoro-1-(4-methoxyphenylsulfonyl)pyrimidin-2(1H)-one
(0.293 g, 0.979 mmol), anhydrous potassium carbonate
(K.sub.2CO.sub.3; 0.271 g, 1.96 mmol), and N,N-dimethylformamide
(DMF; 4 mL), followed by iodomethane (CH.sub.3I; 0.208 g, 1.47
mmol). The reaction vessel was sealed, and the reaction mixture was
warmed to 60.degree. C. and stirred for 4 h. The reaction mixture
was cooled to room temperature, diluted with EtOAc (20 mL), and
washed with water (H.sub.2O; 3.times.10 mL). The organic phase was
dried over MgSO.sub.4, filtered, and the solvent was evaporated
under reduced pressure. Purification by flash chromatography
(silica gel (SiO.sub.2), EtOAc/Hexanes gradient) afforded the title
compound as a pale yellow solid (36 milligrams (mg), 12%): mp
158-162.degree. C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta.
8.01 (d, J=9.22 Hz, 2H), 7.74 (d, J=5.27 Hz, 1H), 7.04 (d, J=9.23
Hz, 2H), 3.90 (s, 3H), 3.31 (s, 3H); ESIMS m/z 314
([M+H].sup.+).
Step 3: Preparation of
5-Fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (I-3)
[0072] A 25-mL screw capped vial was charged with
5-fluoro-4-imino-1-(4-methoxyphenylsulfonyl)-3-methyl-3,4-dihydropyrimidi-
n-2(1H)-one (80.4 mg, 0.257 mmol), trifluoroacetic acid (TFA; 16.0
mL, 215 mmol), and dimethylsulfide (94.0 .mu.L, 1.28 mmol). The
resulting solution was allowed to stir at room temperature for 5.5
h and was then concentrated to dryness by rotary evaporation at
30.degree. C. The crude material was then dissolved in a minimal
amount of methanol (CH.sub.3OH; .about.2 mL) and loaded onto a 5-g
normal phase solid load Isco cartridge, rinsing the source vial
with CH.sub.3OH (3.times.1 mL). The solid cartridge was then dried
under vacuum at room temperature. After drying, the product was
purified by chromatography (4 g SiO.sub.2 column; 0 to 30%
CH.sub.3OH in dichloromethane (CH.sub.2Cl.sub.2) gradient). The
material thus obtained was determined to be the 4-methoxysulfonic
acid salt of the desired product. The free base was obtained by
dissolving the material in CH.sub.3OH (4 mL), adding MP-carbonate
resin (345 mg, 3.03 mmol/g, 4.0 equiv), and allowing to stir at
room temperature. After stirring for 20 h, the solid resin was
filtered off and rinsed with CH.sub.3OH (3.times.1 mL). After
concentration under high vacuum,
5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (35.2 mg,
96%) was obtained as a 95% pure white solid: mp 181-184.degree. C.;
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 7.48 (d, J=4.1 Hz, 1H),
3.22 (s, 3H); .sup.13C NMR (101 MHz, DMSO-d.sub.6) .delta. 152.19
(s), 151.86 (d, J=27.3 Hz), 136.73 (d, J=221.0 Hz), 129.45 (d,
J=26.0 Hz), 28.91 (s).
EXAMPLE 2
Preparation of
1-(3,5-dichlorobenzoyl)-5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(-
1H)-one (Compound 1)
##STR00004##
[0074] In a capped vial,
(E)-trimethylsilyl-N-(trimethylsilyl)acetimidate (157 mg, 0.774)
was added to
5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(111)-one (100 mg,
0.704 mmol) and acetonitrile (1.0 mL) and heated at 70.degree. C.
for 30 min. The solution was cooled to room temperature and
3,5-dichlorobenzoyl chloride (133 mg, 0.633 mmol) was added
dropwise and the contents were stirred overnight at room
temperature. The reaction was concentrated with a stream of
nitrogen. Diethyl ether (Et.sub.2O; 3 mL) was added and the vial
was recapped and shaken briefly. The solids were filtered and
washed with a small amount of Et.sub.2O and air dried to provide
the title compound as a white solid (78 mg, 35%): mp
142-143.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.65
(d, J=5.5 Hz, 1H), 7.56 (t, J=1.8 Hz, 1H), 7.49 (d, J=1.8 Hz, 2H),
3.40 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 166.97,
136.71, 135.23, 135.12, 132.76, 132.37, 127.95, 126.48, 114.66,
114.27, 29.56, 29.01; ESIMS m/z 317 ([M+H].sup.+).
EXAMPLE A
Evaluation of Fungicidal Activity: Leaf Blotch of Wheat
(Mycosphaerella graminicola; anamorph: Septoria tritici; Bayer Code
SEPTTR)
[0075] Wheat plants (variety Yuma) were grown from seed in a
greenhouse in 50% mineral soil/50% soil-less Metro mix until the
first leaf was fully emerged, with 7-10 seedlings per pot. These
plants were inoculated with an aqueous spore suspension of Septoria
tritici either prior to or after fungicide treatments. After
inoculation the plants were kept in 100% relative humidity (one day
in a dark dew chamber followed by two to three days in a lighted
dew chamber) to permit spores to germinate and infect the leaf. The
plants were then transferred to a greenhouse for disease to
develop.
[0076] The following table presents the activity of typical
compounds of the present disclosure when evaluated in these
experiments. The effectiveness of the test compounds in controlling
disease was determined by assessing the severity of disease on
treated plants, then converting the severity to percent control
based on the level of disease on untreated, inoculated plants.
TABLE-US-00001 TABLE 1 Compound number and structure Prepared as
described Compound in Pre- No. Structure Example: cursor(s) 1
##STR00005## 2 As described 2 ##STR00006## 2 4- methyl- benzoyl
chloride, I-3
TABLE-US-00002 TABLE 2 Compound number and analytical data Compound
No. Appearance MP (.degree. C.) Mass .sup.1H NMR .sup.13C NMR 1
White 141.6-142.6 ESIMS .sup.1H NMR .sup.13C NMR Solid m/z 317
(CDCl.sub.3) .delta. 7.65 (CDCl.sub.3) .delta. [M + 2H].sup.+ (d, J
= 5.5 Hz, 166.97, 136.71, 1H), 7.56 (t, J = 135.23, 135.12, 1.8 Hz,
1H), 132.76, 132.37, 7.49 (d, J = 1.8 127.95, 126.48, Hz, 2H), 3.40
114.66, 114.27, (s, 3H) 29.56, 29.01 2 White 103-107 ESIMS .sup.1H
NMR .sup.13C NMR Solid m/z 262 (CDCl.sub.3) .delta. 7.82
(CDCl.sub.3) .delta. [M + H].sup.+ (s, 1H), 7.59 (d, 169.24,
152.53, J = 8.1 Hz, 2H), 148.45, 144.41, 7.55 (d, J = 5.5 138.63,
130.68, Hz, 1H), 7.33- 129.15, 129.10, 7.20 (m, 2H), 115.50,
115.11, 3.40 (s, 3H), 29.49, 21.82 2.42 (s, 3H)
[0077] In each case of Table 3 the rating scale is as follows:
TABLE-US-00003 % Disease Control Rating 76-100 A 51-75 B 26-50 C
0-25 D Not Tested E
TABLE-US-00004 TABLE 3 One-Day Protectant (1DP) and Three-Day
Curative (3DC) Activity of Compounds vs. SEPTTR at 100 ppm SEPTTR
SEPTTR 100 100 Compound PPM PPM No. 1DP 3DC 1 A A 2 A A
* * * * *